Blend compounds of sulfonated polymers and compositions thereof

ABSTRACT

This invention relates to unique and novel blend compounds of an amine neutralized sulfonated elastomeric polymer and an unsulfonated elastomeric or thermoplastic polymer. These compounds can also be blended with fillers and/or oils when the sulfonated polymer is elastomeric. The materials display thermoplastic character.

FIELD OF THE INVENTION

This invention relates to unique and novel blend compounds of an amineneutralized sulfonated elastomeric polymer and an unsulfonatedelastomeric or thermoplastic polymer. These compounds can also beblended with fillers and/or oils when the sulfonated polymer iselastomeric. The materials display thermoplastic character.

BACKGROUND OF THE INVENTION

Recently, a new class of thermoelastic sulfonated polymers has beendescribed in a number of U.S. patents. These sulfonated polymers arederived from polymeric materials having olefinic unsaturation,especially elastomeric polymers such as Butyl and EPDM rubbers. U.S.Pat. No. 3,642,728, herein incorporated by reference, clearly teaches amethod of selective sulfonation of olefinic unsaturation sites of anelastomeric polymer to form an acid form of a sulfonated elastomericpolymer. The olefinic sites of the elastomeric polymer are sulfonated bymeans of a complex of a sulfur trioxide donor and a Lewis base. The SO₃H groups of the sulfonated elastomer can be readily neutralized with abasic material to form an ionically cross-linked elastomer at roomtemperature. However, these ionically cross-linked elastomers may beprocessed like a conventional thermoplastic at elevated temperaturesunder a shear force in the presence of selected preferentialplasticizers, which dissipate the ionic associations at the elevatedtemperatures, thereby creating a reprocessable elastomer.

The basic materials used as neutralizing agents are selected fromorganic amines or basic materials selected from Groups I, II, III, IV,V, VI-B and VIII, and mixtures thereof, of the Periodic Table ofElements.

U.S. Pat. No. 3,836,511, herein incorporated by reference, teaches animproved process for the sulfonation of the olefinic sites of theelastomeric polymer, wherein the improved sulfonating agent is selectedfrom acetyl sulfate, propionyl sulfate and butyryl sulfate. Theneutralizing agents employed to neutralize the acid form of thesulfonated elastomeric polymers are organic amines.

U.S. Pat. No. 3,870,841, herein incorporated by reference, teaches amethod of plasticization of the polymeric backbone of a neutralizedsulfonated plastic polymer by means of a polymer chain plasticizer whichis a liquid compound having a boiling point of at least about 120° F.The polymer chain plasticizer is selected from a dialkyl phthalate, aprocess oil or an organic acid ester. Additionally, a domain plasticizercan be incorporated into the composition, wherein the domain plasticizerreversibly disrupts the association of the sulfonated groups at atemperature of forming.

U.S. Pat. No. 3,847,854, herein incorporated by reference, teaches amethod of improving the processability of neutralized sulfonatedelastomeric polymers by the addition of a preferential plasticizer whichhas at least one functional constituent which exhibits a bond momentwhose absolute value is at least 0.6 Debyes, and must be a liquid at thedesired processing temperature of the neutralized sulfonated elastomericpolymer.

SUMMARY OF THE INVENTION

Sulfonated polymers have been shown to display many of thecharacteristics of a covalently cross-linked elastomer or plasticdespite the fact that these materials are only physically cross-linked.Such materials would be especially useful to employ in blendcompositions, with a variety of other polymers such as polyvinylchloride, polyurethanes, polystyrene, "Phenoxy A", polyethylene andsimilar compositions. However, sulfonated polymers are usuallyincompatible with such compositions except under unusual circumstances.

This invention is concerned with blend compositions of an unsulfonatedelastomeric or thermoplastic polymer with a new class of polymers basedon the chemical combination of sulfonated polymers and anamine-terminated polylactone. As such, these polymers can have many ofthe physical properties of the base sulfonated polymer (such as SulfoEPDM) but also derive many of the desirable features of the polylactone(such as poly-ε-caprolactone). Generally, the sulfonated polymer and thelactone polymer are not truly molecularly compatible and; therefore, arephase separated. Due to the fact that the sulfonated polymer ischemically combined with a novel class of amine terminated lactones, (asdescribed in a copending application) the resulting grafted polymersystem displays some properties of both polymer phases.

Since the polylactones, such as poly-ε-caprolactone, are widely knownfor their unique compatibility behavior, this invention permits thepreparation of polylactone neutralized sulfonated polymers which areuseful in a variety of polymer blends. In the case where Sulfo EPDM isthe base sulfonated polymer, the combination with amine-terminatedpoly-ε-caprolactone provides a "graft" system which can behave as atough and useful thermoplastic elastomer. Such compositions derive theirphysical properties, in part, from the ionic interactions, but mostlydue to the crystalline caprolactone domains which act as physicalcross-links. Such systems can also be modified through the addition ofoils and fillers, as in the case for other sulfonated elastomers. Theresulting materials can, under appropriate conditions, be meltprocessable.

This invention is based upon blend compositions of a thermoplastic orelastomeric polymer with an unsulfonated elastomeric or thermoplasticpolymer based on chemically combining a sulfonated polymer and atertiary amine terminated polylactone composition. The resulting amineneutralized sulfonated polymer compositions have a variety of usesincluding those as diverse as adhesive agents, thermoplastic elastomers,additive uses wherein these materials can be utilized to compatiblizetwo different polymers which are normally incompatible. Thesecompositions can also be blended with fillers and/or oils when thesulfonated polymer is elastomeric. The materials display thermoplasticcharacter.

The neutralized sulfonated elastomeric polymers of this presentinvention are derived from elastomeric or thermoplastic polymers whereinthe elastomeric polymers are derived from unsaturated polymers whichinclude low unsaturated elastomeric polymers such as Butyl rubbers orEPDM terpolymers.

Alternatively, other unsaturated polymers are selected from the groupconsisting of partially hydrogenated polyisoprenes, partiallyhydrogenated polyisoprenes, partially hydrogenated polybutadienes,Neoprene, styrene-butadiene copolymers or isoprene-styrene randomcopolymers.

The expression "Butyl rubber" as employed in the specification andclaims, is intended to include copolymers made from a polymerizationreaction mixture having therein from 70 to 99.5% by weight of anisoolefin which has about 4 to 7 carbon atoms, e.g. isobutylene andabout 0.5 to 30% by weight of a conjugated multiolefin having from about4 to 14 carbon atoms, e.g. isoprene. The resulting copolymer contains 85to 99.8% by weight of combined isoolefin and 0.2 to 15% of combinedmultiolefin.

Butyl rubber generally has a Staudinger molecular weight as measured byGPC of about 20,000 to about 500,000, preferably about 25,000 to about400,000 especially about 100,000 to about 400,000 and a Wijs Iodine No.of about 0.5 to 50, preferably 1 to 15. The preparation of Butyl rubberis described in U.S. Pat. No. 2,356,128 which is incorporated herein byreference.

For the purposes of this invention, the Butyl rubber may haveincorporated therein from about 0.2 to 10% of combined multiolefin;preferably about 0.5 to about 6%; more preferably, about 1 to about 4%,e.g. 2%.

Illustrative of such a Butyl rubber is Exxon Butyl 365 (Exxon ChemicalCo.), having a mole percent unsaturation of about 2.0% and a Mooneyviscosity (ML, 1+3, 212° F.) of about 40-50.

Low molecular weight Butyl rubbers, i.e. Butyl rubbers having aviscosity average molecular weight of about 5,000 to 85,000 and a molepercent unsaturation of about 1 to about 5% may be sulfonated to producethe polymers useful in this invention. Preferably, these polymers have aviscosity average molecular weight of about 25,000 to about 60,000.

The EPDM terpolymers are low unsaturated polymers having about 1 toabout 10.0 wt. % olefinic unsaturation, more preferably about 2 to about8, most preferably about 3 to 7 defined according to the definition asfound in ASTM-D-1418-64 and is intended to mean terpolymers containingethylene and propylene in the backbone and a diene in the side chain.Illustrative methods for producing these terpolymers are found in U.S.Pat. No. 3,280,082, British Pat. No. 1,030,289 and French Pat. No.1,386,600, which are incorporated herein by reference. The preferredpolymers contain about 40 to about 75wt. % ethylene and about 1 to about10 wt. % of a diene monomer, the balance of the polymer being propylene.Preferably, the polymer contains about 45 to about 70 wt. % ethylene,e.g. 50 wt. % and about 2.6 to about 8.0 wt. % diene monomer, e.g. 5.0wt. %. The diene monomer is preferably a nonconjugated diene.

Illustrative of these nonconjugated diene monomers which may be used inthe terpolymer (EPDM) are 1,4-hexadiene, dicyclopentadiene,5-ethylidene-2-norbornene, 5-methylene-2-norbornene,5-propenyl-2-norbornene, and methyl tetrahydroindene.

A typical EPDM is Vistalon 2504 (Exxon Chemical Co.), a terpolymerhaving a Mooney viscosity (ML, 1+8, 212° F.) of about 40 and having anethylene content of about 50 wt. % and a 5-ethylidene-2-norbornenecontent of about 5.0 wt. %. The Mn as measured by GPC of Vistalon 2504is about 47,000, the Mv as measured by GPC is about 145,000 and the Mwas measured by GPC is about 174,000.

Another EPDM terpolymer Vistalon 2504-20 is derived from Vistalon 2504(Exxon Chemical Co.) by a controlled extrusion process, wherein theresultant Mooney viscosity at 212° F. is about 20. The Mn as measured byGPC of Vistalon 2504-20 is about 26,000, the Mv as measured by GPC isabout 90,000 and the Mw as measured by GPC is about 125,000.

Nordel 1320 (DuPont) is another terpolymer having a Mooney viscosity at212° F. of about 25 and having about 53 wt. % of ethylene, about 3.5 wt.% of 1,4-hexadiene, and about 43.5 wt. % of propylene.

The EPDM terpolymers of this invention have a number average molecularweight (Mn) as measured by GPC of about 10,000 to about 200,000, morepreferably of about 15,000 to about 100,000, most preferably of about20,000 to about 60,000. The Mooney viscosity (ML, 1+8, 212° F.) of theEPDM terpolymer is about 5 to about 60, more preferably about 10 toabout 50, most preferably about 15 to about 40. The Mv as measured byGPC of the EPDM terpolymer is preferably below about 350,000 and morepreferably below about 300,000. The Mw as measured by GPC of the EPDMterpolymer is preferably below about 500,000 and more preferably belowabout 350,000.

In carrying out the invention, the elastomeric polymer is dissolved in anonreactive solvent such as a chlorinated aliphatic solvent, chlorinatedaromatic hydrocarbon, an aromatic hydrocarbon, or an aliphatichydrocarbon such as carbon tetrachloride, dichloroethane, chlorobenzene,benzene, toluene, xylene, cyclohexane, pentane, isopentane, hexane,isohexane or heptane. The preferred solvents are the lower boilingaliphatic hydrocarbons. A sulfonating agent is added to the solution ofthe elastomeric polymer and nonreactive solvent at a temperature ofabout -100° C. to about 100° C. for a period of time of about 1 to about60 minutes, most preferably at room temperature for about 5 to about 45minutes; and most preferably about 15 to about 30. Typical sulfonatingagents are described in U.S. Pat. Nos. 3,642,728 and 3,836,511,previously incorporated herein by reference. These sulfonating agentsare selected from an acyl sulfate, a mixture of sulfuric acid and anacid anhydride or a complex of a sulfur trioxide donor and a Lewis basecontaining oxygen, sulfur, or phosphorous. Typical sulfur trioxidedonors are SO₃, chlorosulfonic acid, fluorosulfonic acid, sulfuric acid,oleum, etc. Typical Lewis bases are: dioxane, tetrahydrofuran,tetrahydrothiophene or triethyl phosphate. The most preferredsulfonation agent for this invention is an acyl sulfate selected fromthe group consisting essentially of benzoyl, acetyl, propionyl orbutyryl sulfate. The acyl sulfate can be formed in situ in the reactionmedium or pregenerated before its addition to the reaction medium in achlorinated aliphatic or aromatic hydrocarbon.

It should be pointed out that neither the sulfonating agent nor themanner of sulfonation is critical, provided that the sulfonating methoddoes not degrade the polymer backbone. The reaction is quenched with analiphatic alcohol such as methanol, ethanol or isopropanol, with anaromatic hydroxyl compound, such as phenol, a cycloaliphatic alcoholsuch as cyclohexanol or with water. The unneutralized sulfonatedelastomeric polymer has about 10 to about 200 meq unneutralizedsulfonate groups per 100 grams of sulfonated polymer, more preferablyabout 15 to about 100; and most preferably about 20 to about 80. Themeq. of unneutralized sulfonate groups per 100 grams of polymer isdetermined by both titration of the polymeric sulfonic acid and DietertSulfur analysis. In the titration of the sulfonic acid, the polymer isdissolved in solvent consisting of 95 parts of toluene and 5 parts ofmethanol at a concentration level of 50 grams per liter of solvent. Theunneutralized form is titrated with ethanolic sodium hydroxide to anAlizarin-Thymolphthalein endpoint.

The unneutralized sulfonated elastomeric polymer is gel free andhydrolytically stable. Gel is measured by stirring a given weight ofpolymer in a solvent comprised of 95 toluene-5-methanol at aconcentration of 5 wt. %, for 24 hours, allowing the mixture to settle,withdrawing a weighed sample of the supernatant solution and evaporatingto dryness.

Hydrolytically stable means that the acid function, in this case thesulfonic acid, will not be eliminated under neutral or slightly basicconditions to a neutral moiety which is incapable of being converted tohighly ionic functionality.

Neutralization of the unneutralized sulfonated elastomeric polymer isdone by the addition of a solution of a polycaprolactone polymer to theunneutralized sulfonated elastomeric polymer typically dissolved in themixture of the aliphatic alcohol and nonreactive solvent. Thepolycaprolactone polymer is dissolved in a solvent system consisting oftoluene, optionally containing an aliphatic alcohol. Thesepolycaprolactone polymers are formed by the reaction of ε-caprolactonewith an organic diamine in the presence of a catalyst as described in acopending application U.S. Ser. No. 332,850, filed Dec. 21, 1981. Theanhydrous ε-caprolactone and the organic diamine in the presence of thecatalyst are reacted together in a reaction vessel in the absence of asolvent at a temperature of about 50 to about 200° C., more preferablyabout 75° to about 180° and most preferably about 90° to about 100° C.for a sufficient period of time to effect polymerization.

The reaction of the ε-caprolactone with the diamine can be generallydepicted by the equation ##STR1## wherein n=1 to 500, m=1 to 20, R₁ orR₂ are selected from the group consisting of alkyl and cycloalkyl groupshaving about 1 to about 20 carbon atoms, more preferably about 1 toabout 12 carbon atoms, and aryl groups, and R₃ is selected from thegroup consisting of hydrogen, alkyl and cycloalkyl groups having about 1to about 20 carbon atoms, more preferably about 1 to about 12, and arylgroups and R₄ and R₅ are hydrogen, alkyl, cycloalkyl or aryl groups.Typical, but nonlimiting, examples of useful diamines are:

Catalysts useful in the promotion of the above-identified reaction areselected from the group consisting of stannous octanoate stannoushexanoate, stannous oxalate, tetrabutyl titanate, a variety of metalorganic based catalysts, acid catalysts and amine catalysts, asdescribed on page 266, and forwarded in a book chapter authored by R. D.Lundberg and E. F. Cox, entitled Kinetics and Mechanisms ofPolymerization: Ring Opening Polymerization; edited by Frisch and Rugen,published by Marcell Dekker in 1969, wherein stannous octanoate is anespecially preferred catalyst. The catalyst is added to the reactionmixture at a concentration level of about 100 to about 10,000 parts ofcatalyst per 1 million parts of ε-caprolactone.

The resultant polycaprolactone polymer has an Mn as measured by GPC ofabout 200 to about 50,000 more preferably about 500 to about 40,000, andmost preferably about 700 to about 30,000 and a melting point from belowroom temperature to about 55° C., more preferably about 20° C. to about52° C., and most preferably about 20° C. to about 50° C.

The metal sulfonate-containing polymers at the higher sulfonate levelspossess extremely high melt viscosities and are thereby difficult toprocess. The addition of ionic group plasticizers markedly reduces meltviscosity and frequently enhances physical properties.

To the neutralized sulfonated polymer is added, in either solution or tothe crumb of the unneutralized form of the sulfonated polymer, apreferential plasticizer selected from the group consisting ofcarboxylic acids having about 5 to about 30 carbon atoms, morepreferably about 8 to about 22 carbon atoms, or basic salts of thesecarboxylic acids, wherein the metal ion of the basic salt is selectedfrom the group consisting of aluminum, ammonium, lead or Groups I-A,II-A, I-B and II-B of the Periodic Table of Elements, and mixturesthereof. The carboxylic acids are selected from the group consisting oflauric, myristic, palmitic or stearic acids and mixtures thereof; e.g.zinc stearate, magnesium stearate, or zinc laurate.

The preferential plasticizer is incorporated into the neutralizedsulfonated polymer at less than about 60 parts by weight per 100 partsof the sulfonated polymer more preferably at about 5 to about 40, andmost preferably at about 7 to about 25. Alternatively, otherpreferential plasticizers are selected from ureas, thioureas, amines,amides, ammonium and amine salts of carboxylic acids and mixturesthereof. The preferred plasticizers are selected from fatty acid ormetallic salts of fatty acid and mixtures thereof. The resultantneutralized sulfonated polymer with preferential plasticizer is isolatedfrom the solution by conventional steam stripping and filtration.

The ingredients incorporated into the blend compositions of the presentinvention, in conjunction with the type of elastomeric polymer, thedegree of sulfonation, and the metal counterion of the neutralizedsulfonated polymer and the plasticizer give materials processable byextrusion or injection molding processes into elastomeric articleshaving the desirable physical and rheological properties. These combinedphysical properties and rheological processability characteristics werenot previously obtainable in the aforementioned U.S. patents andapplications previously incorporated herein by reference.

The polymer compositions prepared according to this invention cover avariety of new systems and applications. For example, Sulfo EPDMneutralized with tertiary amine terminated poly-ε-caprolactone canpossess a variety of properties depending on sulfonic acid content andpoly-ε-caprolactone (or PCL) molecular weight. Thus, a high molecularweight PCL (for example, a number average molecular weight of 10,000)coupled with Sulfo EPDM of 30 milliequivalents per 100 grams sulfonicacid content would require about 300 grams of PCL per 100 grams of SulfoEPDM to effect neutralization. Such a composition, therefore, would beabout 75 percent PCL. On the otherhand, the use of a PCL polymer of1,000 molecular weight would result in a neutralized graft ionomer ofabout 23 percent PCL. The physical properties of these two compositionswill obviously vary substantially, depending on the compositions.

The application to which these novel polymers can be put to use isvaried. The PCL/Sulfo EPDM grafts are useful as thermoplasticelastomers, potential adhesives and an approach to compatibilizenormally incompatible polymers such as polyvinyl chloride and ethylenepropylene copolymers or terpolymers, or similarly incompatible systems.

Other types of polymer sulfonic acids suitable in this invention includesulfonated polybutadiene, sulfonated polyisoprene, sulfonated Butyl,sulfonated SBR, sulfonated polypentenomer, etc. Of special interest arepolymers with terminal unsaturation such as polyisobutylene. Typically,this polymer is terminated with an olefin group which can be sulfonatedto provide a long chain polyisobutylene of from 500 to 25,000 inmolecular weight. Sulfonation of this functionality provides a polymerwith a sulfonic acid group at just one end, and which can then beneutralized to provide a polyisobutylene/PCL block copolymer composed ofjust two blocks. These materials can be of special use as potentialcompatibilizers or adhesives between polymers which do not normallyadhere or blend to form compatible blends. Examples of such polymers areButyl rubber and polyvinyl chloride or polyisobutylene andpolyester-based polyurethanes.

The potential list of polymers which can be adhered or blended togetherby the use of these concepts is extensive. Obviously, the list ofpolymers suitable for such uses will depend on the particularPCL/Sulfonated polymer considered. The following list is intended torepresent combined systems for several types of such grafts, asindicated.

                  TABLE I                                                         ______________________________________                                        COMPATIBILITY TABLE FOR SULFO                                                 EPDM/PCL GRAFTS                                                               Column A          Column B                                                    Polymer Phase "Compatible"                                                                      Polymer phase "Compatible"                                  with EPDM         with PCL                                                    ______________________________________                                        Ethylene propylene copolymer                                                                    Polyvinyl chloride                                          Natural rubber    Nitrocellulose                                              cis polybutadiene Low density polyethylene                                    Polypropylene     Phenoxy A                                                                     (the phenoxy resin made                                                       with bisphenol A)                                                             Polyvinyl butyral                                                             Polyester based polyurethanes                               ______________________________________                                    

Those polymers listed in Column A can generally be combined with thosepolymers listed in Column B, when sufficient Sulfo EPDM/PCL graft isused as a compatibilizer. Generally, it is anticipated that amounts of 5to 50 percent of Sulfo EPDM/PCL graft is required to effect thiscompatibilization. Similarly ternary and more complex blends can beconsidered to behave comparably.

Unless otherwise specified, all measurements are in parts by weight per100 parts of sulfonated polymer.

EXAMPLE 1

3.5 g (1 meq.) of a sulfonated EPDM (based on EPDM of 50 percentethylene, 45 percent propylene and 5 percent ENB, sulfonated with acetylsulfate in situ, as described in U.S. Pat. No. 4,221,712 and relatedcases, isolated in methanol as the acid form, and dried in a vacuum ovenat ˜35° C.) containing 29.0 meq. of sulfur per 100 g of polymer, asdetermined by elemental analysis, was dissolved in 66.5 g tolueneovernight to give a 5.0 weight percent solution.

2.1 g (1 meq.) of an N,N-dimethyl-1,3-propane diamine terminatedpolycaprolactone MW 2,100 %N=1.314±0.005 percent prepared as describedin a copending application Ser. No. 332,813, filed Dec. 21, 1981, wasdissolved in 18.9 g of toluene to give a 10.0 weight percent solution.This solution was then added to the highly viscous EPDM polymer sulfonicacid solution prepared above.

Films were cast from the solution of neutralized polymer acid ontoTeflon coated aluminum foil. The solvent was removed by evaporation atambient conditions. The resultant films were a slightly hazy yellow andshowed no visible signs of phase separation. The resulting filmsappeared to be tough and flexible with no evidence of incompatibility.

Thermal mechanical analysis conducted on the polymer sample revealed amajor transition at about -65° C. (EPDM Tg) and a second transition atabout 38° C., identified as the crystalline melting point for thepolycaprolactone phase.

EXAMPLE 2

On a roll electric mill at about 130° C., the following blend compoundswere made by fluxing the neutralized sulfonated polymer with variousother polymers at the temperature indicated.

The compositions of these blends are listed in the following Table II.

                                      TABLE II                                    __________________________________________________________________________                 2-0                                                                              2-1 2-2 2-3 2-4 2-5 2-6 2-7 2-8                               __________________________________________________________________________    Neutralized sulfonated                                                                     100                                                                              50  50  50  50  25  75  25  75                                elastomeic polymer of                                                         Example 1                                                                     Polyvinylchloride -                                                                           50              75  25                                        (Diamond Shamrock 450)                                                        Polystyrene - Styron 666                                                                          50                                                        Dow Chemical                                                                  Polypropylene -         50                                                    Exxon CD-430                                                                  Polyethylene -              50          75  25                                Exxon LD-600                                                                  Mark 275 (antioxidant)                                                                        1               1   1                                         Mill Temperature °C.                                                                   130 130 170 130 130 130 130 130                               Pressed film at 325° F.                                                                good                                                                              brittle                                                                           poor                                                                              good                                              Solubility in toluene                                                                         insol-                                                                            insol-                                                                            insol-                                                                            insol-                                                                            insol-                                                                            insol-                                                                            insol-                                                                            insol-                                            uble                                                                              uble                                                                              uble                                                                              uble                                                                              uble                                                                              uble                                                                              uble                                                                              uble                              Tensile at yield            1236        1478                                                                              944                               Tensile at break                                                                           1256                                                                             1100        1220                                                                              1956                                                                              821 1555                                                                              1060                              Elongation   590                                                                              10%         490%                                                                              20% 50% 577%                                                                              475%                              __________________________________________________________________________

What is claimed is:
 1. A polymer blend which comprises a blend of:(a) asulfonated polymer which has about 10 to about 200 meq. of sulfonategroups per 100 grams of said sulfonated polymer, said sulfonate groupsbeing neutralized with a polycaprolactone polymer having the formula:##STR2## wherein n=1 to 500, m=1 to 20, R₁ or R₂ is selected from thegroup consisting of alkyl and cycloalkyl groups having about 1 to about20 carbon atoms and aryl groups, and R₃ is selected from the groupconsisting of hydrogen, alkyl and cycloalkyl groups having about 1 toabout 20 carbon atoms and aryl groups, and R₄ and R₅ are selected fromthe group consisting of hydrogen, alkyl, cycloalkyl and aryl groups andsaid polycaprolactone polymer has an M_(n) as measured by GPC of about200 to about 50,000 and a melting point from below room temperature toabout 55° C., wherein said neutralized sulfonated polymer is formed froman elastomeric polymer selected from the group consisting of Butylrubber and an EPDM terpolymer, said component having about 5 to about 50percent of said sulfonated polymer neutralized with saidpolycaprolactone polymer; and (b) an unsulfonated thermoplastic orelastomeric polymer.
 2. A polymer blend according to claim 1 wherein R₁and R₂ are an alkyl group and R₃ is hydrogen.
 3. A polymer blendaccording to claim 1 wherein either R₁ or R₂ is a methyl group and R₃ ishydrogen.
 4. A polymer blend according to claim 1, wherein R₁ and R₂ areboth methyl groups and R₃ is hydrogen.
 5. A polymer blend according toclaim 1, wherein R₁, R₂, and R₃ are methyl groups.
 6. A polymer blendaccording to claim 1 wherein said EPDM terpolymer consists essentiallyof about 40 to about 75 wt. % of ethylene, of about 10 to about 53 wt. %of propylene and of about 2 to about 10 wt. % of a nonconjugated diene.7. A polymer blend according to claim 6, wherein said nonconjugated dienis selected from the group consisting of 1,4-hexadiene,dicyclopentadiene, 5-alkylidene-2-norbornenes, 5-alkenyl-2-norbornenesand tetrahydroindene.
 8. A polymer blend compound according to claim 7,wherein said nonconjugated diene is 5-ethylidene-2-norbornene.
 9. Apolymer blend according to claim 1 wherein said unsulfonated polymer isselected from the group consisting of ethylene propylene copolymer,natural rubber, as polybutadiene, and polypropylene.
 10. A polymer blendaccording to claim 1 wherein said unsulfonated polymer is selected fromthe group consisting of polyvinylchloridde, Phenoxy A, polyvinylbutyral,polyester-based polyurthenate, low density polythylene andnitrocellulose.